Treatment of gas liquor



' Dec." 22' 1925.

I;56'6',"795 LEROY w. NEFF-NER ET AL TREATMENT OF GAS LIQUOR 2 Sheets-Sheet 2 Filed Dec. 16. 1924 l V L ft d I INVENTORS, WMM J4 0606( l i others skilled in the art to, which it apper- Patented Dec. 22, 1925.

UNITED STATES BEST AVAiLABLE CGP:

1,566,795 PATENT oFElcE..

LE ROY WILBUR HEFFNER, O1" E AST N ORRISTOWN TOWNSHIP, MONTGOMERY COUNTY,

AND WILLIAM TIDDY, OF JEFFERSONVILLE, PENNSYLVANIA.

TREATMENT 'or erasi LIQU'OR.-

- Application filed-,December 16, 1924.v Serial No; 756,193.

-To all '1o/mm. if may concern.:

Be it known that we, LE Roi' IV. III-:Ernia: and `WILLIAM Tmm', both' citizens of the United States, residing?y at. East Norristown- Township, county` of Montgomery, State of- Pennsylvania, `and Jeti'ersonville, county of Montgomery, State of Pennsylvania, .respectively, have invented certain new and useful Improvements in the Treatment of'vGas Liquor; and we do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable tains to make vand use the same. This invention relates to the treatment of gas liquor and ammoniacal liquor from gas plants or coke ovens whereby the waste liquor from the ammonia stills can bedisposed ot without the objections incident t0 f present methods -ot disposal. The process et the invention, in its broader aspects, .is also applicable tor the separation and recovery ot' phenols from other waste liquors, containing the phenols in small amounts.

After the treatment et gas liquor, for the recovery of ammonia therefrom, the Waste liquor'trom the ammonia stills contains ini'- purities, particularly those ot a phenolic character, which, even though present in .relatively minute amounts, are objectionable in streams or other bodies of` Water from which drinking water is obtained, particularly it the drinking;- water is subjected to a chlorination treat-nient. These objections to still waste liquor are well recognized, with theresult that the discharge of such liquor into streams or other bodies of water, is in many cases prohibited, and special means or provisionsare necessary for the treatment or disposal of this waste liquor, such as the pumping of the liquor to special collection or treatment basins or to waste land where .it is not a source of contamination to city water supplies. laste liquors from other sources, such as those t'rom the manufacture ot' phenolic resins or' condensation products, i are similarly objectionable.

Numerous attempts and proposals have been made to treat still waste liquor to free it trom its objectionable impurities, but these methods. so far as we are aware,have been only partially successful, and have not brought aboutv a suiiicient purification of the waste liquor. l.Y

As distinguished from such prior pro.r

posals to treatthe waste liquor, the present invention relates to an improved method of treatmg the gas liquor in connection with the removal of ammonia therefrom, so that v the )vaste liquor is directly obtained in a state suiiciently free from objectionable ime purities to permit it,- after the usual dilution, to be discharged directly into'streams Without the resulting objections incident to the similar discharge of presentday Waste liquor. f Y

In' the customary methods oftreating gas .liquor from coke oven `plantsor from gas plants for the distillation of ammonia thererom, the gas liquor is fed without preheatingA ingo the ammonia still', inthe first or free'ammonia'sectionpof which the free ammonia is largely driven ol,`a fter-which the' liquor is mixed with lime and heated'by steam to set, freethev combined ammonia which passes into the free ammonia section of the'still and is driven oit along with the free ammonia from this section. In aqua ammonia and concentrated ammonia :liquor plants, Where the liquor is preheated to drive oit' hydrogen sullid and carbon dioxide before it is fed, into the ammonia still, de- Y phlegmators are provided to c'ool the ammonia vapors and to separate' water vapor therefrom in order to reduce the burden on the condensers and absorbers and'to avoid dilution, the' ammonia driven oit from the free ammonia section of the still being passed through the dephlegmator and the' temperature of the liquorin the still and in the dephlegmator being maintained sutticiently low so that Athe ammonia gas will be driven oi in a relatively concentrated state, free from any large amount of water vapor.

In our in'vestigration-ot` the operation of such ammonia stills, we have observed that the phenols tend to be combined with and driven 'off with the ammonia but are prevented from being so driven oit by'the low le have found, however, that it thevtem- .i

perature ofthe liquor inthe still is maintained sufficiently high, e. g.,V between 98 and 100 C. or higher, and lif a suliicient amount otianimoniais present and is driven foti, substantially all of Vtheuphenol can be driven off-with the ammonia. and'tliereby 'prevented from 'being carried down into contact with the lime andvfi'o'm bcingfixed -r.

into contact wth the lime, so thatthe lime 'has no opportunity of combining with the phenolsand of retaining them in the liquor. The improvedf process ofthe present in-A yention, in its broader-aspects, can be' carried outin present day ammoniastills, providedv the; liquor in the still is'eapable oft being mater should not maintained at aT-'sgiiiicientlyphigh tempera,- O

tur bove 498 C. y ,ere such stills are provided with de hlegmators, the dephlegcooled to a'lowtemperature, but' should be kept at asuiciently high temperature sothat the-vapors are not cooled A-below 98 C., and preheaters or other heating meansv such; as steaincoils, should be4 provided ier maintaining the tem' eratuic of the li uor4 at the inlet ofthe stil 'sutiic'iently hi out the process of the invention, and the to ,insure the volatilization and escape yo the phenols orof the henolates. Our investigations indicate that te phenols are combined,flargely if not entirely, as ainnionium phenolatcs, which are more volatile than the phenols themselves, and which A are readily removed when `a suiiicient amount df ammonia. assed through the hot solution and when t ie liquor is maintained at a' sufiiciently 'high temperature.

We have, however, provided'an improved apparatus, specially adapted lfor carrying process can 'be carried outgwith particular advantage in such apparatus, although the process, in its broader. aspects, snot limited to any a paratus.

'In or er to insure that'the phenol is suh-` stantially all driven olli' with the ammonia,`

' we have found it necessary to provide oi' in- Y sure a sufficient amount of ammonia, usually in excess of that normally present in the liquor. In the case pf gas liquors particularly rich in ammonia, the ammonia content of the liquor may itself be sutiicient to insure driving off the phenols in accordance with the present invention; but Where the weaves assi AvAiLA'eLE coe.l

gas-liquors do not. themselves contain a sufl ticient amount of ammonia, we have found it necessary to provide additional ammonia to assistin driving out the plienols.

required for the purpose may advanta- Ve have found that the added ammonia vgeously bea' part of that giyen off from the ammonia still itself. This ammonia, ,how-

ever, carries the `phenols with it, and its direct return to the still would reintioduce the phenols or phenolates. To avoid this, we subject the ammonia coming oli from the still to'apurilication treatment tol free it froiirthe phenolsor phenolates -which it `carries, and we obtain in thisway airainnionia suiiiciei'itlyl free to permit its return to the still to increase the ammonia content in the free ammonia portion of the-still. The ammonia given ott' from the still, in the process of the lpresent invention, also carries with it a much laigei' contcnt of steam or water vapor than the ammonia normally escaping from ammonia stills.l We find that. the ammonia, after uriiication from .phenols, canadvantagcous y be subjected to a. -dephleginatingaction and 'al considerable amount of the water vapor condensedtherefrom together with some of the ainiiioniii.

This aminoniacal water can advantageously' be returned to the still to increase the ammonia content of the liquor tlieieii1,'and to vcorrespondingly increase the ammonia passing upwardly' through the. free ammonia section of thestill. Where the amount of ammonia returned in this way as ammoniacal liquor is not suiiicient, further amounts of ammonia gas can be returned to thestill to vinsure enough ammonia to complete the `driving off the phenols or phenolatcs from 'the still.

Instead of obtaining the. ammonia from the stills themselves, in the manner just inentioned, aminon/a from another source may, if available, be used to increase the i nimonia content of the liquor in the stilhiand the ammonia escaping from the still itself may be puriiied and employed, for example, for the pioduc'tionof aqua-ammonia or ofam.- inonium sulphate. AWe consider it. more advantageous, however, to utilize the'an'nnonia,

or a part of the ammonia, given oli' fromthc AStill itself, after purification to free it from orphcnolates with 'which it is Y i r the phenols .admixed y u Where the amount of phenol in the gus liquoris small, the amount may'not befof sufficient value to warrant its recovery, although ,the amount may heA Suiiicientso that, if not removed, the waste liquor would he objectionable. In such cases, Iwe may purity the: ammonia and free it from the small amounts of phenol without' recovering the phenol, thereby obtaining the ammonia in a purified state for absorption lor for use in the process.

lili) i 'lotion of phenolate obtained,`and the water .ltageously be'rcturned to the still, as above wtajins the required amount ot sodium phenndeterioration.

" separated from the ammonia gas Vby cooling,

l I .sEsTAVAiLAeLE cori le find, li'oucver, that the aiuouut oli for the practice of theiprooessof'theinvenplienolcontained iu gasliquor is'often suflition. ',Iu the ilraivings,'l"ig. l--sliows a someciently high to make its recovery profitable;` what diagramm v and we find that the improved process of ment of the apparatus yand Fig, 2.*slio/wsl outhe -prese-nt invention enables' the, plienols a somewhat enlarged scalefone 4form of *he Ato be recovered in asimple and advantageainmonialstill` itself. ous manner, and as a by-product, so to speak, v Refer-rino lfirst toy `of the main process of purification of the "gas liquor.A

Fignl, itwill be seen that the apparatus includes the 'prelieater l l for the 'gas liquor with a release pipe 2 hav- The separation of the phenol fromA the in, r valve therein, aiid' 'with lan outlet pipe -ammonia4 can be eflccted' in different ways, 5 -fo`r vconveying thegras liquor to the top of forexample, by passing thucombined'vapois the 'free ammonia still 4 into )vliich it enters atical. form and arrange-J.4

from the ammonia still througha' washer.' through the branch pipes v6v. and A7.' l The.

containing lime. caustic soda, absorbent carvapor or ammonia outlet pipe troniL the free hon, -or`otlier suitable absorbent'inediuin 'for ammonia still is l'indica-tedv at` S. The still the ieiuovaLot-tlie plienols and tarryacids. has the usual lime legjf) which is connected 'The absorbent containing the phenols and with the fixed ammonia still /lOtlii-ough the -t-ai'ry acids combined therewith may, if the pipe 11 .--The ammonia gasfroin' the fixed recovery lot thphenolsaiid tarry acids is .ammonia still passes through'the pipe12 to not to be efiected;\.;be disposed 4of.in any `the free :ammoniastill in 'the'usual way. Y

suitable "wayg Wlierem the phenol -is to be. The linie leer is provided .witlia heating'coil reciwere'dg: the absorbent medium should be '13 having ste-ani `regulating valve 14; While "of a character ivhiel'i with permit 'the ab. the fixedv ammoniastill has-as'tea'in'supply srbed or combined phenol tl,-he.si ibseqlui itl y pipe 15 with controlling'"valve"16therein. separated'therefrom. For exan'fple'y'iising 'llieiwaste 'liquor yfrom the fixed ammonia; caustie soda. sodium plienolate, etc., ivill -be still is drawn' off through the pipe 17 having l' foi-ined. and the phenol can Ybe subsequently control valvev 18 therein. The 'apparatus recovered from the sodium phenolate soluthus far described may betliesaie as the' tion by acidification 'and distillation. f ordinary..amnionia still, `or the jstill 'inay" be' ln applying` the phenol separation'and rcmodified, e. gaas illustrated-in Fig. 2. coveiy in combination with the treatment of- The spplyiif gas liquor 'enters ythrough the gas liquor, in the process-of the present the pipe 1,9 and through one or the. other invcntiomth'e ammonia 'and admixed vapors or both of the' branch pipes 20 and 21 to thev from theammonia.l still can be passed prelieater. Suitable regulating'valves 22,*23, through a Washercoiitaini1ig\ a solution QLtand'23are provided. Tlie'liraneh pipeA 2l caustic soda kept ata sufficiently high temhas-a coil 24 arrangedin the dephlegmator perature to prevent dilution from the water 28 to 'cool the gases passingr therethrough, vapor condensing'rom the combined vapors. the liquor beingr itself somewhat heatedA in 4Uy passing the gases through 'such a washer y .this way. l. v and then through av condenserl or dephlegf The vapors from the ammonia still enter niator. the phenols'andvtarry acids can be the phenol absorber 26 which may be of effectively absorbed -and a'concentrated soany Suitable constmciim! i-.U bring the' gages into intimate contact with the absorbent.A ,vapor can be separately and subsequently- Forexgmple, an valkali soltimi muy be provided in'this washer. The washer has an outlet pipe -27 with control valvel29 therein for drawing off the alkali phenola-te solution The' ammonia g'as after purification passes througli the pipe 30 to the deplileg- .mater V2S where the gases are cooled and Water vapor islargely separated. The amr'noniacal liquor tlius'condensed may. be re- .ileavingrv the ammonia gas free from excess finoisture. for subsequentA absorption; while- 'the separated ainmoniacal water can advaninentioned. As soon as the caustic soda'eonlate, it. isremoved and -phenol and tariv acids recovered. for example, b v acidification and distillation. or b v'vother recovery process. The plienolate may, for example. be treated witl'i'carbfn dioxide, or other acid or uitrecake, with resulting separation of the oils, which inayjbe recovered by steam distillation, using indirect steam distillation in a vacuunistill, and with a condenser constructed of suitable material tov prevent undue The invention will be further described in connection 'with the accompanying: drawings which illustrate an apparatus adapted l turned .through thepipe to thefixed arnmonia still 10.v

. After passing' through the depl 28, the-ammonia. gas. treed frouia considerable portion otY its adn'iixed water-vapor, passes through the pipe 3l, liavingvalve 33 therein, to the saturator or 'Y absorber.

. l y ildfrmator part of 'this gas-may be Vreturned through 125 the pipe 32. havingva-lve 34 therein, to the bottom of the free' ainmoniasti'll, a suitable 'pump 37 being provied for forcing this l aininniainto the free 4vammonia still.

'v `One suitable' form of ammoniastill is illustrated -more in detail in Fig.' 2, the general features of this still being indicated by.the same reference characters 'usedl in Figgfl.v The -ree ammonia still'4 and the fixedv ammonia still are `made up of suitablc'baie arrangements for insuring' that upwardl flowing ownwardly throughthis portion of the ammonia will 'be progressively. riven off' from the liquor. The free, ammonia driven oif -from -the' fixed ammonia still passes through the pipe 1,2 into the lower part' of the free Aammonia. still and passes countercurrent to the hot liquor the still. -By introducing additional am monia through the pipev 22,` the' amount of ammonia passing upwardly through this still can be increased sufiiciently to insure that allor substantially 'all of the phenols' and tar acids aredriven oil' when theproper temperature is maintained.- The gas liquor from the :bottom of .the freeammonia still passes down through the lime leg where the Vreaction with lime takes place, and the 1i uor then flows to the fixed-"ammonia still all of the i monia vapors; The upper; portion of the free ammonia still becomes a countercurrent scrubber, and, by maintaining the gas liquor at a suiiicientlv high temperature, above 98 C., removal of a considerable portion of the ammonia and phenolate will take place before the liquor reaches the lower portion of the free ammonia still, while the added ammonia from the fixed ammonia still,or recycled after purification to the bottom ,of the free 'ammonia still, will complete the driving ofi" .of the phenolic compounds as phenolates..

AIn Fig. 2, two outlet pipes, 8 and 8, are indicated for the ammoniacal vapors escaping from the still. The outlet pi e 8 permits all of t'he vapors from the still) to pass to the phenol absorber,` as illustrated in the arrangementof Fig. 1. Theoutlet pipe 8* is connected with a dephlegmator by means of which tlie' t emperature of the ammoniacalvaporslcan be somewhat reduced before these vapors pass to the phenol absorber. In 'the'` operation ofthe ammonia still` the tempera# ture may be maintained considerably abovel 98 (land even above 103 G. Particularly at the latter land Ahigher'temperatures, a

large amount of water v por comes oil with ,the ammonia. 'By cooling the vaporsto-a' temperaturebelow' 103 C., i f e., between 103 C. and 98 .C ,a considerable portion bf 'the excess water vapor can'be condensed' 'ammonia still.. A

The'A gas liquor is preheated to 98 C. or above before entering the ammonia still to' BEST AvaiLAeL- ,coe/Y' from .the vaporslbefore they pass ytothe phenol absorber. In the apparatus of Fig.

2, the outlet pipe v8" leads toa reflux cooler' `o'r dephlegmator 8b, 'from .which the cooled vapors escapes'at'SQand the reflux condensate is returnedto-tlie ammonia still through the pipe 8?. l vSuitable valvesinfthe pipes 88 and 8" permitl controlling the flow of vaporsA so that theyv pass either through the outlet pipe 8 or' through the outlet pipe'8a and dephlegmafor.- 1`hedephlegmator may he cooled by` water .which is `regulated Ain vamount and temperature sothat the vapors are not cooled=belowv98 C., thereby preventing recondensation or vreabsorption of phenolate. A l

In theoperation ofthe process. in the apparatus'illus'trat'ed, vthe ammonia stills ma be'operated in much the usual Way, but

wit a higher temperature in the free anxmonia still andparticularly at its outlet, and also ammonia isintroducedif necessary into the. free ammonia st ill in suilicient amount to insure that-allor substantially p'henol's are removed with the ammonia.

The'admiaed.vaporsl lfrom the ammonia still pass to the purifier or phenol absorber, where thev ammonium phenolates are decomposed, e. g. by caustic soda,` and sodium phenolatesrformed'. The ammonia and admixed 'watervapor then pass to the cooler or dephlegmator 28A where Water vapor and some ot 'the ammonia are condensed and the ammonia'then escapes to the saturator or may be inpartrecycled through' .the pipe 32 to the free'` ammonia still.` The condensate lfrom vthe condenser or dephlegmator 28 is returned throughthe pipe 35 to the fixed assistin preventing reabsorption ofphenolate vapors when' passing through the still. Ihe liquor passing through the free' ammoniastill is also kept ata temperature of at least 4,98 CJ and preferably somewhat higher, and-it is Vbroughtnto contact with ammoniavaporsrof su'icient volume to re-I act with the phenols, forming ammonium phenolates, which we have found to be more readil volatile than-the phe-nols4 themselves, and w 'ich'are not reabsorbedwhen vthe tem? perature of the. liquor"is'about 98- C. and when a .sufiicient.. amount of ammonia is resent'. The rec climr of ammonia. made possible bythe apparatus illustrated, enables any desired amountof the-ammonia to befrecycled` so that the presence `of sufcient ammonia can be insured .for securing complete or substantially complete driving oli of the phenols as phenolates. The pur l lication of the ammoniaesca-ping from'the still makes possible its return and enables mee,

l the henols to be recovered from it as one Y animoniacal-Iiqiior formed as aA condensate in Lit) , 4moniaA is evolved and passed the condenser `or'`dephlegmatorifl passes to` the fixed ammonia section -ivhe'refthe am into the bottom of the freesection. f- 1; In the operation'of thev apparatus of 2, the temperature maybe maintained inV part by preheatingitlie gasliquor to. atemperature of 98. C. o r higher, and in-'part` by the refluiecondenser or dephlegmator .8", where this dephlegnii'itor is used; -The teinperature of the liquor in the still includiii the liquor at. the top or liquor inlet portion of the still,`is maintainedab'ove' 98 C; and may be several degrees higher than that temperature. If the temperature of the escaping vapors "is too high, so that their water vapor content is excessive, they` may becooled in the dephlegmatorV `8"'andifa-considerable portion of the i'vater vapor removed therefrom beforethey pass to/the phenol absorber.

The process of the` present-invention eniibles as much as` 99.5% or `more of the phenols originally present-in the gas-liquor to be removed therefrom with 'tlie ammonia, so that the waste' liquor i'lowing-ffrom the ammonia still' contains l'such insignificantv traces of phenoll that, when diluted, they' are'l unobjeetionable and can be discharged into; wat'er courses. In some cases, it may not'be necessary toeffect complete removal of the pi-enols from the gas liquors but tlieprocess.

of' tlie present invention enables such re'- inoval to be eilected with substantial comA pleteness', or with a-sutlicient approximation 1o con'ipleteiiess toiemove tl'ienuisance from ilie waste liquor from the still. For ex- :iinpleythe 4removal 4of around 98 to 99% of the plienols present in the liquor can readily be. effected.

As an example of the application of the process, a gas liquor containing as liigli :is 2.3 grams of phenols per liter was treated `with maintenance of the liquor at a tempcr- :iture of about 99.5"D C; and an amount of ammonia was added' in the form ot concentrated ammonia solution equal to that ot gas liquor treated. The v Waste liquor" contained only 0.0203 gram of phenol per liter, corresponding to :i removal of 99.5% ot t-li.e phenols present inthe gas liquor. In a similar run using about two-thirds as much ammonia, a removal of 98.2%` of the4 plienols present iiithe gas liquor was effected.

It will thus be seen that the present invention provides a new and improved method oftreating gas liquor. in which the treatment ot the liquorlii'ing's about the removal o.

, supply y ,eEsTm/Aimsteooev' `"reis 5 phenols,"et c., and in whichthis treatment and. removal takes place before or after or during the passage of the liquor ,through the ammonia` still. It ivill also be seen that the' process prevents the 1 phenols -from coming in contact with'the lime which would otherwise-combine j with them fand hold them so 1 that they would contaminate'the Waste liquor. The ,fpresentfmethod is thereforeof a different character frommetliods vottreating the -wastezliquor itself for .the removal or partial-removal offits phenolic content. .r' v

The present process moreoveren'ables sub;

stantiallyl.omplete removal of the objec- I tionable-phenolic constituents-'to be ellected,

f eliminatiomof ul 'to 98 or 99% or more being easily accomplis ed; whereas 'with the best methods of treatingl the residual liquor itself,

.a removal 'ofabout '80% of the plienols is approximatelyfthe.highest etiiciency obtainable in so far asfvve Vare aware by any method.

which did not `involve -an unreasonable ex` pense or'equ'ipment or operation; andsucli ajremovalof 8,0% 4is not sufficiently high to allowl the treated-fstill-waste` to be diverted into vrivers without resultingcomplaints from neighboring consumers. f

It .will furthe'rbe seenthat the present-invention can lbe Acarriedoutin apparatus such as that uzliich is 'now vused `for ammonia stills .with only such modification as may be needed fo'r insuring 'the maintenance .of a'suflficiently, lhigh temperature of the liquor in the still 'and at its outlet, and -with the added equipment necessary for providing an added to remove the' lime, sludge, 4etc.,'for example,

by means of settling tanks or thickeners. If

further decolorization of the liquor is' de, sirable, this canbe effected by a decolorizing treatment, for example, by treatment ot the liquor with tlue gases.

It w'ill bc evident that where the gasfliquor containsa considerable amount of phenol,

the present invention enables-it tobe recovered :is a valuable product of the process.

`From the standpoint ot phenol i'ecovery,rit

may not be of importance to cllect complete removalsof phenol from the liquor to an extent that will make the liquor unobjectiona blc; but it is one advantage of the process vand apparatus of the present invention that with the recycling ot a sulicient amount of of ammonia, -which may advanta ammonia and with the maintenance of the proper temperature in the free ammonia still, substantiallyall of the phenol can be lll removed'from the'liquor andhrecovered as al product of the process.

The process of. the'present invention requi'res' a .relatively small outlay for 'added plant equipment, and but little added attention on the part' of tli'eoperaton jIt is there# fore well adapted for use. in conjunction with- 'present' day lammonia stills; and yitenables --liquor 4now produced cannot be discharged Vinto streams,fbecause of its .pollutin effect,

'and where it requires special disposa as by pumping a considerable distance, the present process results in a waste liquor sufficiently vand over, supplying only such pure to. permit it tobe discharged intov streaniswith the avoidance-ofsuch nuisance.

While we'have. described the invention more particularly for the. treatment of gas l nor, and -while the invention 'isfof special va ue for such 'treatmeiit,` and. enables the present nuisancetof still waste-liquors,to be overcome, the procsis applicable for the treatment of other' wasteliquors, andA particul'arl phenol is employed, andI which contain phenol in small amounts. ,The rocess can thus be employed to advanta e or the recovery 'of phenol present in sma l amounts in waste liquors-from the manufacture of phenolic resins or condensation products.

In the .treatment of waste liquors which do not contain ammonia, b ut which contain phenols, the liquorv is heated to a 4tempera.- ture of 98 (Lor higher and sutlicient ain-x` inonia is supplied thereto to combine with 'the lphenols to form volatile phenolatesand -to supply a sutiicient amount of ammonia in addition to carry away the phenolates therewith. While the ammonia m ,Y be obtained from any available source an ?lilded tp the phenol-containing liquors, theprocess, when once started, may be made self-contained by recovering and refusing theammonia over added amounts as will make up for loss in the proccss. The ammonia may tlgiiis be added to the phenol-containing liquor and theliquor preheated and Vsubjected to distillation, or the liquor may be first preheated and then introducedinto a ,still and there brought into contact with the ammonia.. In a cyclic pi'occss'of operation, for example, in an apparatu's` such as that illustrated in Fig. 1,I

the ammonia may recycled repeatedly, with urification to -separate phenolic compoun s therefrom in the manner hereinbefore described.l The same -am'monia may thus be used continuously iu the process with liquors 'from processes'in which BEST Avait/isis com A. continuous purilication and recycling of the puritiedfanimona. By maintaining a sufncientl ammonia, substantially complete recovery high temperature, i. e. above 98 C;, -an by recycling a lsuiiicient amount of of phenol "can'be, obtained. Where waste liquors containismall but important pei-centagesof ph'enol, such that the phenol is difi'icult to recovernby other methods,.the proc ess of the present invention enables the phenol to 'be recovered with substantial com# pletion..` Thephenols are, moreover, ,recovcred atrelatively smallA expense,"the main elements of expense, otherfthan-cost of equipment, being the heat required for-heating the liquor, the cost of alkali forabsorbing the phenol, and the attention of the loperator-in `operating the apparatus. Inasmuch as the wastel liquor. from the process leaves the still at a high temperature, this may be employed to preheat Vthe li uor' supply-to the apparatus, through suita le countercurrent heat interchan ers, and the cost of heat'n thereby reduce In addition to the value o the phenol' recovered `from' waste liquors in this way,`the process has the important ad# vantageof freeing-the waste liquor from phenolic compounds to such an extent as to permit it to he discharged into streams with Y Y 1. The process of recovering pheiiols from liquors containing' the same .in small amounts, which comprises subjecting the liquor to a temperature of'98 C. or higher,

Ill() in the'presence 'of suilicient ammonia to drive otf theA phenol as phenolate.

2. The process of recovering phenols from liquors containing'. the sainel in small 'nmounts, which comprises reheating the liquor to a temperatureof a out 98 C. ort

small rent of 'ammonia vapors, the temperature'of 1|' the liquor higher.

4. The process of recovering plienols from liquors containing the same in small amounts, which vcomprises pfeheating the liquor toa temperature oa out 98 C. or

higher, and subjecting 'the preheated liquor to the action of ammonia while maintaining being maintained at 98 C.l ort the liquor at a temperature of 98 C. or

higher, whereby the phenolsA are converted into -ammonium phenolate and removed iu vapor form with the ammonia.

Aturning the ammonia for further vuse inthe(- lratmeht oth'e liquor. f

6. The processlof recovering phnols from liquors containing .the vsaine 1n,;.js1na l1 amounts, which comprises subjectm'g such liquor to distillation' with ammonia at a teinperature -of 9 C."or higher,the ammonia. being present 1n sufiicientainount to combine.

withv the phenol `and carry, otlthe resulting -phenolatel in vapor form, separating the phenolate from the ammonia and' returningvthe ammonia .to the still.v 7. The proeessof recovering phenols from liquors containing the same in small amounts, which comprises reheating the liquor. to a ten'iperature ofia out 98"C.' or higher, introducing the preheated liquor `int0 a still, and causing`it to pass therethrough countercurrent to ammonia vapors, t'lieiteinperature of the liquor being inaintainedat 98 C. or higher,1separatingphenolic compounds from the ammonia and returning the ain'monia for furthelfcircultion -countercurrent to the liquor.

8, The process of recovering phenols front liquors containing the same in small amounts,A

which comprises subjecting'the liquortoa temperatureot 98 C. or higher, in the presence'of suflicicnt ammonia to drive .ol the phenol as phenolate, treating the resulting vapors of ammonia and ammonium'phenoh :itcwith caustic alkali to form alkali phenolate and toset free tlie ammonia 4from the v ammonia plieiiolate.

9. The process of recovering plieiiols from liquors containing the saine in Snialljalii'ounts. which comprises subjecting such liquor to distillation ivith ammonia at a temperature ot' 98 C. or higher, the, ammonia beingA present in suflicient amount toonibinc. with the phenol and carry ott the resulting phenolate in vapor foi-untreating the resulting vapors of ammonia and ammonium phenolate with caustic alkali to torni alkali plienolatc and to set l'i'ee the ammonia vliroiiilhe.

amii'ioiiium pluiiiolale, and returning the 'uiuiiioiiia for the treatment ot tui-ther amountsI of liquor.

l0. 'lhe proqess ot' treating gas liquor con-A taining phenolic impurities which comprises subjecting the same to distillation for the.' recovery of ammonia therefrom. and iiiaui.

with .the ammonia. 1

fthe ammonia, and separating the phenolate ossi' AvAitAstEcosv" taining plicnolicimpurities which comprises subjecting the saine to distillation in a free ammonia still for the removal vof tree aininonia tl'ieretro'in, then setting free the fixed ammonia'. and `passing it through the free am- 70 .inonia still,' passing additional. ammonia. through the free 'ammonia still, vandiniain taining the temperature' of the liquor at the vtop of thefree ammonia still aty about 98 C. 'or higher, whereby phenoljs driven ott' 75 fromA the' free ammonia stillas phenolate The process of treat ing gas 'liquor v`containing phenolic iimpurities which comprises subjecting'th'e saine, to distillation in a free ammonia-still for the reinovalof .free ainnionia therefrom, then setting free the fixed ammonia *and passing it through the free ammonia still, and maintaining the tenipcratureof the liquor in the tree ammonia still 'at about 98 or higher,-wherebyl phenol is driven oil' from the free ammonia still as i'ihenolatcj with the ammonia, 'suliif cient annuonia being introduced intqthe free ammonia still to i' insure substantially com- 90 'plete volatilization of the phenol-with the ammonia.` f 1 3. Thepro'cess of treating gas liquor conf taining phenolic impurities which comprises p're7heating. the liquor, introducing the pref 95 .heated liquor into a free ammonia still'and subjcct'ing'the same todistillation' there-iin. the liquor-in the free ammonia still .being` maintained at a temperature inexcessi ofv about 98 C. and aisulicieut amount of aini 100 monia being-presenttherein to effect removal of substantially all otthe phenol' iis' plie-- nolate withtlie ammonia, and separating the phenolute from the ammonia.v i

"14. The process of treating gas liquor conl taining phenolic impurities which comprises pre-heating the 'liquoiy introducing the preheated liquor into 'au aiiiiiiouja still` the liquor .in the upper portion ol' which is innintaincd at a ten'iperaturepf 9S" C. or higher,' 116 and' subiecting the' liquor t-liereiu to the action of sufficient aiuinonia'do reiuoie substantially all ot' the phenol as'phenolate with from the ammonia. 115

15. The process of treating gas liqiior'containing phenolicl i'inpurities which comprises subjecting the` saiiieto distillation with' maintenance of the liquor at a temperature in excess ot about 98 C. and in the preseiicu 120 ot' a'sulticient amount of ammonia to remore. phenolic compounds With the ammonia, and freeing the ammonia from phenolic compounds by; passing the' adniixed Vgases through an absorbent for the phenolic com 125 pounds. 16. r1 he process of treating gas liquoA Ao taining phenolic impurities'ivhich compili subjecting the same to distillation infanuin iiionia still for the recovery of ammonia4 13 therefrom. the temperaturi.E of both 'the liquor and'. the escaping vapors and gases vfrom the ammonia. stillbemg inA excess of about .98 C. todrivefot-phenplio compounds withV the ammonimftre'ating the admlxed vapors and gases to separat/ephenolic .compounds therefrom, and returninga part 'of the resulting pnrlfied ammonia/to the thcrefron'u the temperature of. both #the liquor' and the escaping vuporsand gases from the ammonia still being` in excess of about 98 vC.- to drive off phenolic com.

" pounds with the ammonia, treating the admixed vaporsfandgases to separate phenolic compounds therefrom, andreturning a part of the resulting purified ammonia to the ammonia still,Y the 'amount of ammoniaso returned being suilicientto insure substantiallv complete removal of phenolic 'compounds from thestill' with the ammonia."

18. The process of treating gas liquor-containing phenolic impurities which comprises pre-heating .the same, introducing' the preheated liquor into :1n-ammonia still, the

liquor in the upper portion of which is maintained .at a temperature in excess 4of about 98 C. to effect removal ofphenolic compounds with the ammonia, separating the phenolic compounds from the ammonia, and

returning a portionofthe'resuiting purifiedammoniato the ammonia still, the amount` of ammonia so returned being sufficient with mme BEST A vArLAsLE- com maintaining the'liquor in the upper portion l mote the removal of phenolic compounds Y from the liquor.

21. The process of treating gas liquor containing phenolic Aimpurities which coinprises subjecting the same to distillation in an ammonia still, maintaining the liquor in the stilliat atemporature'around.98 to 100 C. or higher to drive ofi` phenolic compounds with the ammonia, passing the admixed phenolic a-nlfa'mmonia vapors through an absorber containing an absorbent, to remove the plie-- vncli'c compounds, introducing a portion of the resulting purified'- ammonia into the ammonia stillY to provide an c xcess of anmonia therein to promote the removalof phenolic compounds, and .recovering the plieno'ls from the absorbent.

22.; lThe process oftreating gas liquor cons i taining Hphenolic impurities' which comprises subjecting the same to 'distillation in an ammonia still in which the liquor is maintained at .a temperature in excess -of about 98"C..to insure the driving ofi' of phenolic'compunds with the'ammonia, purifying the resulting ammonia from phenolic compounds subjecting the .purilied ammonia and admixed water vapor to a condensing orv dephlegmating operation to condense a considerable portlon of the Water vapor to'- gether with part of the ammonia, and returning the resulting ammoniacal water to the that lpresent in the Still t0 insure th'SubStilIl- `stillto increase the ammonia. content theretially complete removal of the phenolic com-f of,

pounds. v

19. The process of treating gas liquor con- 23. The'process o`f treating-gas liquor containing phenolic impurities which comprises` taining phenolic impurities which comprises subjecting the same to distillation in .an pre-heating the liquor, introducing the pre#- ammonia still inwhch the liquor is mainheatcd liquor into.a free' ammonia still, the tained at a temperature in excess of about4 liquor inthe upper portion of which is main- 98 C- t0 insure thedriving on' of phenolic tained at a temperature in excess of about 98 (l. to cfectremoval -of. phenolic com-`` `resultingv ammonia from phenolic compounds with the ammonia,v` sub]ec'tmg the\-pounds,' su'ecting the purified ammonia sufficient to insure substantially complete re 4 moval of the phenolic compounds from the` liquor in the free ammonia still before the liquor is treated for the setting frecof fixed ammonia.

20. The process of treating gas liquor containing phenolic impurities which comprises A pre-heating the liquorVA introducing the preheated liquor into an ammonia still and subjecting thesame to distillation' therein and com ounds with the ammonia, purifying the and admix Water vapor to a condensing or dephle ating operation to condense u" lll() lll) considerab e portion "of the water vaporml` gether with partoffthe ammonia, and returning theresulting vammoniacal water to thereof, a. portion of theuncondensed purii'ed ammonia being also returned to the still to .further increase .the ammonia coutent of 'the liquor-therein.

' 24. The method of treating gas liquor con.- tainin phenolic impurities which comprises .tlie.'still to increase the. ammonia 'content subjec ingl the same to distillation in an am-.

monili'7 stlll having a free ammonia section and ga fixed ammonia section, subjecting the liquor vaft/er'plissage through thefiee ammonasectionf' to the action of reagents iso BEST'AVAILABLE COPY ivliioli will set .tree the lixed ammonio, maintaining the temperature of the liquor in the ammonio section of the still in excess of about 980 C. to insure driving oil' of plie nolio compounds with the ammonia, purifying the resulting ammonia from the aoeompenying phenolic compounds, subjecting the purified ammonia to a cooling or de plilegmating-operation to condense-a considerable portion of the admixed Witten vapor together with some ammonia, returning the yesulting zuninoniecel liquor to the fixed :munoniuportion of the still, and also ieturning a part of the uneoudensed purified ei'ninoniu gas to the free ammonia, sectionA of the still, the amount of ammonia so ifetnincd being` sui'iicient to insure substiim tizilly complete. removal of phenolic eornpounds with the ammonia before the'liquoi' ireziohes the chemical reagents which set 'free the fixed. ammonia.

25. The method of recovering plienols from gas liquor which comprises subjecting4 tures.

`LE ROY "WILBUR HEFFNER. vT/VM. TIDDY. 

